Substituted thiazolines and their use for controlling animal pests

ABSTRACT

The invention relates to novel substituted thiazolines of the formula (I)                    
     in which 
     Ar 1  and Ar 2  each represent independently of one another optionally substituted phenyl, 
     processes for their preparation, and their use for controlling animal pests.

The invention relates to novel substituted thiazolines, processes fortheir preparation, and to their use for controlling animal pests.

It is already known that certain oxazoline derivatives have insecticidaland acaricidal properties (cf. for example EP-A-0 345 775 or EP-A-0 432661).

However, the potency and/or persistency of these prior-art compounds isnot entirely satisfactory in all fields of application, in particularwhen used against certain organisms or at low application rates.

The invention provides novel substituted thiazolines of the formula (I)

in which

Ar¹ and Ar² each represent independently of one another optionallysubstituted phenyl.

The invention further provides a process for preparing the novelsubstituted thiazolines of the formula (I) by reacting

a) oxazolines of the formula (II)

in which

Ar¹ and Ar² each have the abovementioned meaning with a sulphurizingagent, optionally in the presence of a diluent;

or by reacting

b) thiazolines of the formula (Ia)

in which

Ar¹ has the abovementioned meaning and

Ph represents optionally substituted halogenophenyl

with boronic acids of the formula (III)

Ph¹—B(OH)₂   (III)

in which

Ph¹ represents optionally substituted phenyl

in the presence of a base, optionally in the presence of a catalyst andin the presence of a diluent.

Furthermore, it has been found that the novel substituted thiazolines ofthe formula (I) are highly suitable for controlling animal pests, inparticular insects, arachnids and nematodes, encountered in agriculture,in forestry, in the protection of stored products and of materials, andin the hygiene field.

Surprisingly, the substituted thiazolines of the formula (I) accordingto the invention have a considerably higher activity against animalpests than the prior-art compounds of a similar structure.

Formula (I) provides a general definition of the compounds according tothe invention.

Preferred substituents or ranges of the radicals mentioned in theformulae given hereinabove and hereinbelow are illustrated below.

Ar¹ preferably represents phenyl which is optionally substituted by oneto five identical or different substituents from the group consistingof:

halogen, nitro, cyano, hydroxyl, amino,

C₁-C₆-alkyl,

C₁-C₆-alkoxy,

C₁-C₆-alkylthio,

C₁-C₆-alkylsulphinyl,

C₁-C₆-alkylsulphonyl,

C₁-C₆-halogenoalkyl,

C₁-C₆-halogenoalkoxy,

C₁-C₆-halogenoalkylthio,

C₁-C₆-halogenoalkylsulphinyl,

C₁-C₆-halogenoalkylsulphonyl,

C₁-C₆-alkoxy-C₁-C₆-alkyl,

C₁-C₆-alkylamino,

di-(C₁-C₆-alkyl)-amino,

and phenyl, benzyl, benzyloxy, phenethyl, phenethenyl, phenethinyl,phenoxy or phenylthio, each of which is optionally substituted inparticular in the phenyl moiety by one to five identical or differentsubstituents from the group consisting of halogen, C₁-C₄-alkyl,C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthioor C₁-C₄-halogenoalkylthio.

Ar² preferably represents phenyl which is optionally substituted by oneto five identical or different substituents from the group consistingof:

halogen,

C₁-C₁₈-alkyl,

C₁-C₈-alkoxy-C₁-C₈-alkyl,

C₁-C₈-halogenoalkoxy,

C₁-C₄-halogenoalkyl,

C₁-C₁₈-alkoxy which is optionally interrupted by a further 1 to 3 oxygenatoms,

C₁-C₁₈-alkylthio,

C₁-C₈-halogenoalkylthio,

tri-C₁-C₈-alkylsilyl,

phenyl-di-C₁-C₈-alkylsilyl,

3,4-difluoromethylenedioxo,

3,4-tetrafluoroethylenedioxo,

a benzo-fused group,

a fused C₄-alkanediyl group,

benzyliminooxymethyl which is optionally substituted by C₁-C₄-alkyl,C₃-C₆-cycloalkyl or halogen,

cyclohexyl or cyclohexyloxy, each of which is optionally substituted byC₁-C₆-alkyl, C₁-C₆-alkoxy, cyclohexyl or phenyl,

pyridyloxy which is optionally mono- or disubstituted by identical ordifferent substituents from the group consisting of halogen, C₁-C₄-alkylor C₁-C₄-halogenoalkyl,

and phenyl, phenyl-C₁-C₆-alkyl, phenethenyl, phenethinyl, phenoxy,phenylthio, phenyl-C₁-C₆-alkyloxy or benzylthio, each of which isoptionally substituted in particular in the phenyl moiety by one tothree identical or different R¹ and/or optionally substituted inparticular in the phenyl moiety by one or two identical or different—OR².

R¹ preferably represents halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy.

R² preferably represents hydrogen, or C₁-C₁₂-alkyl, C₃-C₁₂-alkenyl, orC₃-C₁₂-alkinyl, or C₁-C₆-halogenoalkyl having one or more fluorineand/or chlorine atoms, or C₃-C₆-cycloalkyl orC₃-C₆-cycloalkyl-C₁-C₄-alkyl, each of which is optionally mono- orpolysubstituted in the cycloalkyl moiety by identical or differentsubstituents from the group consisting of:

halogen, C₁-C₄-alkyl, C₂-C₄-alkenyl which is optionally mono- orpolysubstituted by halogen, and phenyl or styryl, each of which isoptionally mono- or polysubstituted, in particular in the phenyl moiety,by halogen;

or represents C₄-C₆-cycloalkenyl or C₄-C₆-cycloalkenyl-C₁-C₄-alkyl, eachof which is optionally mono- or polysubstituted by identical ordifferent halogen and/or C₁-C₄-alkyl substituents;

or represents phenyl-C₁-C₄-alkyl or naphthylmethyl, each of which isoptionally mono- or polysubstituted in the aryl moiety by identical ordifferent substituents from the group consisting of:

halogen, C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl having one or more fluorineand/or chlorine atoms, C₁-C₁₂-alkoxy and C₁-C₁₂-halogenoalkoxy havingone or more fluorine and/or chlorine atoms;

or represents the radical —COR³.

R³ preferably represents C₁-C₁₂-alkyl, or C₁-C₁₂-alkoxy, orC₃-C₁₂-alkenyl, or C₃-C₁₂-alkenyloxy, or represents C₃-C₆-cycloalkyl,C₃-C₁₀-cycloalkyloxy or C₃-C₁₀-cycloalkyl-C₁-C₆-alkoxy, each of which isoptionally mono- or polysubstituted in the cycloalkyl moiety byidentical or different substituents from the group consisting of:

C₁-C₄-alkyl, halogen, C₁-C₄-halogenoalkyl having one or more fluorineand/or chlorine atoms and C₂-C₄-halogenoalkenyl having one or morefluorine and/or chlorine atoms;

or represents phenyl or naphthyl, each of which is optionally mono- orpolysubstituted by identical or different substituents from the groupconsisting of:

halogen, C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl having one or more fluorineand/or chlorine atoms, C₁-C₁₂-alkoxy and C₁-C₁₂-halogenoalkoxy havingone or more fluorine and/or chlorine atoms;

or represents the radical —NR—R⁵.

R⁴ preferably represents hydrogen or C₁-C₁₂-alkyl.

R⁵ preferably represents C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl having oneor more fluorine and/or chlorine atoms, or C₃-C₆-cycloalkyl orC₃-C₆-cycloalkyl-C₁-C₄-alkyl, each of which is optionally mono- orpolysubstituted in the cycloalkyl moiety by identical or differentsubstituents from the group consisting of:

C₁-C₄-alkyl, halogen, C₁-C₄-halogenoalkyl having one or more fluorineand/or chlorine atoms and C₂-C₄-halogenoalkenyl having one or morefluorine and/or chlorine atoms;

or represents phenyl or phenyl-C₁-C₆-alkyl, each of which is optionallymono- or polysubstituted, in particular in the phenyl moiety, byidentical or different substituents from the group consisting of:

halogen, C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl having one or more fluorineand/or chlorine atoms, C₁-C₁₂-alkoxy and C₁-C₁₂-halogenoalkoxy havingone or more fluorine and/or chlorine atoms;

or represents the radical —C(R⁶R⁷)—C(R⁸)═NOR⁹.

R⁶ and R⁷ are identical or different and preferably represent hydrogenor C₁-C₄-alkyl.

R⁸ preferably represents hydrogen, C₁-C₄-alkyl or C₃-C₆-cycloalkyl whichis optionally mono-, di- or trisubstituted by identical or differentsubstituents from the group consisting of C₁-C₄-alkyl, halogen orC₁-C₄-halogenoalkyl.

R⁹ preferably represents C₁-C₄-alkyl.

Ar¹ particularly preferably represents phenyl which is optionallysubstituted by one to five, in particular one to three, identical ordifferent substituents from the group consisting of:

F, Cl, Br,

nitro, cyano, hydroxyl, amino,

C₁-C₄-alkyl,

C₁-C₄-alkoxy,

C₁-C₄-alkylthio,

C₁-C₄-alkylsulphinyl,

C₁-C₄-alkylsulphonyl,

C₁-C₄-halogenoalkyl,

C₁-C₄-halogenoalkoxy,

C₁-C₄-halogenoalkylthio,

C₁-C₄-halogenoalkylsulphinyl,

C₁-C₄-halogenoalkylsulphonyl,

C₁-C₄-alkylamino,

di-(C₁-C₄-alkyl)-amino,

and phenyl which is optionally substituted by one to three identical ordifferent substituents from the group consisting of F, Cl, Br,C₁-C₄-alkyl, C₁-C₄-alkyl which is substituted by one to six identical ordifferent substituents from the group consisting of F and Cl,C₁-C₄-alkoxy, C₁-C₄-alkoxy which is substituted by one to six identicalor different substituents from the group consisting of F and Cl,C₁-C₄-alkylthio and C₁-C₄-alkylthio which is substituted by one to sixidentical or different substituents from the group consisting of F andCl.

Ar² particularly preferably represents phenyl which is optionallysubstituted by one to five, in particular one to three, identical ordifferent substituents from the group consisting of:

F, Cl, Br,

C₁-C₁₈-alkyl,

C₁-C₆-alkoxy-C₁-C₈-alkyl,

C₁-C₆-alkoxy which is substituted by one to six identical or differentsubstituents from the group consisting of F and Cl,

C₁-C₂-alkyl which is substituted by one to five identical or differentsubstituents from the group consisting of F and Cl,

C₁-C₁₈-alkoxy and —(OC₂H₄)₁₋₃—O—C₁-C₆-alkyl,

C₁-C₁₅-alkylthio,

C₁-C₈-alkylthio which is substituted by one to six identical ordifferent substituents from the group consisting of F and Cl,

tri-C₁-C₆-alkylsilyl,

phenyl-di-C₁-C₆-alkylsilyl,

3,4-difluoromethylenedioxo,

3,4-tetrafluoroethylenedioxo,

a benzo-fused group,

a fused C₄-alkanediyl group,

the groupings

 cyclohexyl or cyclohexyloxy, each of which is optionally substituted byC₁-C₄-alkyl, C₁-C₄-alkoxy, cyclohexyl or phenyl,

pyridyloxy which is optionally substituted by one or two identical ordifferent substituents from the group consisting of F, Cl or CF₃,

and phenyl which is optionally substituted by one to three identical ordifferent R¹ radicals and/or optionally substituted by one or twoidentical or different —OR² groupings.

R¹ particularly preferably represents fluorine, chlorine or bromine.

R² particularly preferably represents hydrogen, or C₁-C₆-alkyl, orC₃-C₁₂-alkenyl, or C₃-C₆-alkinyl, C₁-C₄-halogenoalkyl having two or morefluorine and/or chlorine atoms, or C₃-C₆-cycloalkyl orC₃-C₆-cycloalkyl-C₁-C₄-alkyl, each of which is optionally mono- orpolysubstituted in the cycloalkyl moiety by identical or differentsubstituents from the group consisting of:

fluorine, chlorine, bromine, C₁-C₂-alkyl, C₂-C₃-alkenyl which isoptionally mono- or polysubstituted by fluorine and/or chlorine andphenyl and styryl, each of which is optionally mono- or polysubstitutedin particular in the phenyl moiety by fluorine and/or chlorine,

and C₄-C₆-cycloalkenyl and C₄-C₆-cycloalkenylmethyl, each of which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of fluorine and chlorine,

and phenyl-C₁-C₄-alkyl which is optionally mono- or polysubstituted inthe phenyl moiety by identical or different substituents from the groupconsisting of:

fluorine, chlorine, C₁-C₄-alkyl, halogenomethyl having one or morefluorine and/or chlorine atoms, C₁-C₄-alkoxy and C₁-C₄-halogenoalkoxyhaving one or more fluorine and/or chlorine atoms, and the radical—COR³.

R³ particularly preferably represents C₁-C₄-alkyl, or C₁-C₄-alkoxy, orC₃-C₆-alkenyl, or C₃-C₆-alkenyloxy, or C₃-C₆-cycloalkyl,C₃-C₆-cycloalkyloxy or C₃-C₆-cycloalkyl-C₁-C₄-alkyloxy, each of which isoptionally mono- or polysubstituted in the cycloalkyl moiety byidentical or different substituents from the group consisting of:

C₁-C₂-alkyl, fluorine, chlorine., C₁-C₂-halogenoalkyl having 1 to 5fluorine and/or chlorine atoms and C₂-alkenyl having 1 to 3 fluorineand/or chlorine atoms,

or phenyl which is optionally mono- or polysubstituted by identical ordifferent substituents from the group consisting of:

halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl having 1 to 5fluorine and/or chlorine atoms and C₁-C₄-halogenoalkoxy having one ormore fluorine and/or chlorine atoms, or the radical —NR⁴—R⁵.

R⁴ particularly preferably represents hydrogen or C₁-C₂-alkyl.

R⁵ particularly preferably represents C₁-C₄-alkyl or phenyl or benzyl,each of which is optionally mono- or polysubstituted in the phenylmoiety by identical or different substituents from the group consistingof:

halogen, C₁-C₂-alkyl, C₁-C₂-halogenoalkyl having 1 to 5 fluorine and/orchlorine atoms and C₁-C₂-halogenoalkoxy having 1 to 5 fluorine and/orchlorine atoms,

or the radical —C(R⁶R⁷)—C(R)═NOR⁹.

R⁶ particularly preferably represents hydrogen or C₁-C₃-alkyl.

R⁷ particularly preferably represents hydrogen or C₁-C₃-alkyl.

R⁸ particularly preferably represents hydrogen, C₁-C₃-alkyl orC₃-C₆-cycloalkyl which is optionally substituted by one or two identicalor different C₁-C₃-alkyl groups or halogens.

R⁹ particularly preferably represents C₁-C₄-alkyl.

Ar¹ very particularly preferably represents phenyl which is optionallysubstituted by one to four, in particular one or two, identical ordifferent substituents from the group consisting of:

F, Cl, Br, nitro, cyano, hydroxyl,

C₁-C₄-alkyl,

C₁-C₂-alkoxy,

C₁-C₂-alkylthio,

C₁-C₂-alkylsulphonyl,

C₁-C₂-alkyl which is substituted by one to five identical or differentsubstituents from the group consisting of F and Cl,

C₁-C₂-alkoxy which is substituted by one to five identical or differentsubstituents from the group consisting of F and Cl,

C₁-C₂-alkylthio which is substituted by one to five identical ordifferent substituents from the group consisting of F and Cl,

C₁-C₂-alkylsulfonyl which is substituted by one to five identical ordifferent substituents from the group consisting of F and Cl,

C₁-C₂-alkylamino,

di-(C₁-C₂-alkyl)-amino,

and phenyl which is substituted by one or two identical or differentsubstituents from the group consisting of F, Cl, Br, C₁-C₂-alkyl,C₁-C₂-alkyl which is substituted by one to five identical or different For Cl, C₁-C₂-alkoxy, C₁-C₂-alkoxy which is substituted by one to fiveidentical or different substituents from the group consisting of F andCl, C₁-C₂-alkylthio and C₁-C₂-alkylthio which is substituted by one tofive identical or different substituents from the group consisting of Fand Cl.

Ar² very particularly preferably represents phenyl which is optionallysubstituted by one to three, in particular one or two, identical ordifferent substituents from the group consisting of:

F, Cl, Br,

C₁-C₁₈-alkyl,

C₁-C₆-alkoxy-C₁-C₈-alkyl,

C₁-C₈-alkoxy which is substituted by one to six identical or differentsubstituents from the group consisting of F and Cl,

C₁-C₂-alkyl which is substituted by one to five identical or differentsubstituents from the group consisting of F and Cl,

C₁-C₁₈-alkoxy and —(OC₂H₄)₁₋₃—O—C₁-C₆-alkyl,

C₁-C₁₅-alkylthio,

C₁-C₈-alkylthio which is substituted by one to six identical ordifferent substituents from the group consisting of F and Cl,

tri-C₁-C₆-alkylsilyl,

phenyl-di-C₁-C₆-alkylsilyl,

3,4-difluoromethylenedioxo,

3,4-tetrafluoroethylenedioxo,

a benzo-fused group,

a fused C₄-alkanediyl group,

the groupings

 cyclohexyl or cyclohexyloxy, each of which is optionally substituted byC₁-C₄-alkyl, C₁-C₄-alkoxy, cyclohexyl or phenyl,

pyridyloxy which is optionally substituted by one or two identical ordifferent substituents from the group consisting of F,. Cl and CF₃,

and phenyl which is optionally substituted by one or two identical ordifferent R¹ radicals and/or optionally monosubstituted by —OR²groupings.

R¹ very particularly preferably represents fluorine, chlorine orbromine.

R² very particularly preferably represents hydrogen, or methyl, ethyl,propyl, butyl, pentyl, hexyl, or propenyl, butenyl, pentenyl, hexenyl,or propinyl, butinyl, pentinyl, or one the groups: —CHF₂, —CF₂CHFCl,—CF₂CH₂F, —CF₂CHF₂, —CF₂CCl₃, —CF₂CHFCF₃, —CH₂CF₃, —CH₂CF₂CHF₂,—CH₂CF₂CF₃, —CF₂—CHF—CF₃, or one of the cycloalkyl groupings:

 or one of the cycloalkenyl groupings:

 or one of the cycloalkylalkyl groupings:

 or one of the cycloalkenylalkyl groupings:

 or one of the phenylalkyl groupings:

 or the radical —COR³.

R³ very particularly preferably represents methyl, ethyl, propyl, ormethoxy, ethoxy, propoxy, butoxy, or cyclopropyl, cyclohexyl, orcyclohexyloxy, or phenyl, 2-chlorophenyl, 3-chlorophenyl,2,6-difluorophenyl, 2-trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl,2,4-dichlorophenyl, 3,4-dichlorophenyl, or the radical —NR⁴R⁵.

R⁴ very particularly preferably represents hydrogen.

R⁵ very particularly preferably represents methyl, ethyl or phenyl whichis optionally monosubstituted by chlorine or represents the radical—C(R⁶R⁷)—C(R⁸)—NOR⁹.

R⁶ very particularly preferably represents hydrogen, methyl or ethyl.

R⁷ very particularly preferably represents hydrogen, methyl or ethyl.

R⁸ very particularly preferably represents hydrogen, methyl, ethyl orcyclopropyl, cyclopentyl or cyclohexyl, each of which is optionallysubstituted by one or two identical or different substituents from thegroup consisting of methyl, ethyl, i-propyl, fluorine, chlorine orbromine.

R⁹ very particularly preferably represents methyl, ethyl, n- ori-propyl.

The hydrocarbon radicals mentioned above in connection with thedefinition of the compounds according to the invention, such as alkyl oralkenyl, can—even in connection with hetero atoms, such as alkoxy—be ineach case straight-chain or branched as far as this is possible.

The abovementioned general or preferred definitions of radicals orillustrations can be combined with each other as desired, that is to saycombinations between the respective general and preferred ranges arealso possible. They apply both to the end products and to thecorresponding precursors and intermediates.

Preference according to the invention is given to the compounds of theformula (I) which contain a combination of the meanings mentioned aboveas being preferred (preferable).

Particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningsmentioned above as being particularly preferred.

Very particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningsmentioned above as being very particularly preferred.

Preference is given to compounds of the formula (IA)

in which

A, D, E, G and H represent the phenyl substituents mentioned above asbeing preferred, particularly preferred and very particularly preferredfor Ar¹, in particular where

A represents hydrogen, fluorine, chlorine, bromine, methyl, methoxy,trifluoromethoxy, methylthio or methylsulfonyl,

D represents hydrogen, methyl, methoxy, fluorine or chlorine,

E represents hydrogen, fluorine or chlorine,

G represents hydrogen, fluorine, chlorine, bromine, methyl, t-butyl,trifluoromethoxy, trifluoromethylthio or dimethylamino and

H represents hydrogen, fluorine, chlorine, methyl or methoxy,

R¹ and R² each have the meanings given above as being preferred,particularly preferred and very particularly preferred,

n is 0 or 1 and

m and o each are independently of one another 0, 1 or 2.

Preference is further given to compounds of the formula (IB)

in which

Ar¹ represents the phenyl radicals below:

and

R² has the meanings given above as being preferred, particularlypreferred and very particularly preferred excluding alkyl, representingin particular halogenoalkyl or in particular halogen.

Besides the preparation examples, specific examples of the compounds ofthe formula (I)

include:

Ar¹ Ar²

If process (a) is carried out using for example2-(2,6-difluorophenyl)-4-(4-trifluoromethoxybiphenyl-4-yl)-2-oxazolineas starting material and phosphorus pentasulphide as sulphurizing agent,then the reaction of the process according to the invention may beillustrated by the following scheme:

If process (b) is carried out using for example2-(2-chlorophenyl)-4-bromophenyl-2-thiazoline and4-(1-difluoro-2-difluoro-eth-1-yl-oxy)-phenylboronic acid as startingmaterials, then the reaction of the process according to the inventionmay be illustrated by the following scheme:

The oxazolines required as starting materials for carrying out theprocess (a) according to the invention are defined in a general way bythe formula (II).

The oxazolines of the formula (II) are known (cf. for example EP-A-0 345775, EP-A-0 432 661, WO-A 95/04726 or WO-A 95/19350) or they are thesubject-matter of our own, still unpublished applications (cf. GermanPatent Applications 4 428 536 dated Dec. 08, 1994 and 4 435 716 datedJun. 10, 1994) and/or can be obtained by the processes mentioned thereinin a conventional and known manner.

The thiazolines required as starting materials for carrying out theprocess (b) according to the invention are defined in a general way bythe formula (Ia).

Ph represents bromo-, iodo- or chlorophenyl which can be substituted byone or two identical or different substituents, in which case preferred,particularly preferred or very particularly preferred substituents arethe radicals already specified above in connection with the descriptionof the compounds of the formula (I) as preferred, particularly preferredor very particularly preferred for R¹.

The thiazolines of the formula (Ia) are compounds according to theinvention obtainable by employing process (a).

The boronic acids also required as starting materials for carrying outthe process (b) according to the invention are defined in a general wayby the formula (III). In the formula (III), Ph¹ represents phenyl whichis optionally substituted by one to three, preferably one or two,identical or different R¹ and/or —OR², R¹ and R² having preferably,particularly preferably or very particularly preferably those meaningsalready specified above, in connection with the description of thecompounds of the formula (I), as preferred, particularly preferred orvery particularly preferred for these substituents.

The boronic acids of the formula (III) are generally known compounds oforganic chemistry and/or can be obtained by generally known methods.

Preferred sulphurizing agents for carrying out the process (a) accordingto the invention are: phosphorus pentasulphide or Lawesson's Reagent[2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-dithione].

Preferred diluents for carrying out the process (a) according to theinvention are hydrocarbons, such as toluene, xylene, tetralin, hexane orcyclohexane.

Reaction temperatures may be varied over a relatively wide range in thepractice of the process (a) according to the invention. Generally, thereaction is carried out at temperatures between 0° C. and 200° C.,preferably between 20° C. and 150° C.

In the practice of process (a) according to the invention, generallybetween 1 and 3 mol, preferably between 1 and 2 mol, of sulphurizingagent are employed per mole of oxazoline of the formula (II). Work-up iscarried out using customary methods.

Suitable diluents for carrying out process (b) according to theinvention are all organic solvents inert under the reaction conditionsgiven. If appropriate, they can be employed in a mixture with water.Preferably used are hydrocarbons, such as toluene, xylene, tetralin,hexane and cyclohexane, halogenated hydrocarbons, such as methylenechloride, chloroform, chlorobenzene and o-dichlorobenzene, alcohols,such as methanol, ethanol, glycol, the isomeric propanols, butanols andpentanols, ethers, such as diethyl ether, diisopropyl ether,dimethoxyethane, tetrahydrofuran and dioxane, nitriles, such asacetonitrile or butyronitrile, amides such as dimethylformamide,sulphoxides such as dimethyl sulphide, and sulpholane.

Suitable bases for carrying out the process (b) according to theinvention are all customary acid acceptors. Preference is given to usingtertiary amines, such as triethylamine, pyridine, diazabicyclooctane(DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN) andN,N-dimethylaniline, further to alkaline earth metal oxides, such asmagnesium oxide or calcium oxide, and also alkali metal carbonates andalkaline earth metal carbonates and alkali metal hydrogen carbonates,such as sodium carbonate, potassium carbonate, calcium carbonate andsodium hydrogen carbonate, alkali metal hydroxides, such as sodiumhydroxide or potassium hydroxide, and also alkoxides, such as sodiumethoxide or potassium tert-butoxide.

If appropriate, the process (b) according to the invention is carriedout in the presence of a catalyst. Suitable catalysts are for example:tetrakis(triphenylphosphine)palladium; palladium-IIacetate/tri(o-tolyl)phosphine; palladium-II chloride, -IIacetate/triphenylphosphine; bis(triphenylphosphine)palladium-IIchloride; and Pd/C/triphenylphosphine.

Reaction temperatures may be varied over a relatively wide range in thepractice of the process (b) according to the invention. Generally, thereaction is carried out at temperatures between 0° C. and 150° C.,preferably between 0° C. and 100° C., or at the boiling point of thesolvent used.

In the practice of process (b) according to the invention, generallybetween 1 and 3 mol, preferably between 1 and 1.5 mol, of boronic acidof the formula (III) and, if appropriate, between 0.01 and 0.2 mol,preferably between 0.05 and 0.1 mol, of catalyst are employed per moleof thiazoline of the formula (Ia), the catalyst being preferably chargedinitially and the thiazoline being added under a stream of inert gas,such as, for example, a stream of argon. Work-up is carried out bycustomary methods.

The active compounds are suitable for combating animal pests, inparticular insects, arachnids and nematodes, encountered in agriculture,in forestry, in the protection of stored products and of materials, andin the hygiene field, and have good plant tolerance and favourabletoxicity to warm-blooded animals. They may preferably be employed ascrop protection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Pediculus humanus corporis,Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Spodoptera litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofnannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Latrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Apelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp.

The compounds of the formula (I) according to the invention inparticular have an excellent insecticidal and acaricidal action.

They can be used particularly successfully for controllingplant-damaging insects and mites.

They have a very strong action for example against mustard beetle larvae(Phaedon cochleariae), caterpillars of the diamondback moth (Plutellamaculipennis), caterpillars of the owlet moth (Spodoptera frugiperda),aphids (Myzus persicae) and also against the spider mite (Tetranychusurticae) and the fruit tree red spider mite (Panonychus ulmi).

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension emulsionconcentrates, natural and synthetic materials impregnated with activecompound and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. Suitable liquidsolvents are essentially: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

Suitable solid carriers are for example ammonium salts and groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates;suitable solid carriers for granules are: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; suitable emulsifying and/or foam-formingagents are: for example non-ionic and anionic emulsifiers, such aspolyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as protein hydrolysis products;suitable dispersing agents are: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphates, carbamates, carboxylates,chlorinated hydrocarbons, phenylureas and substances produced bymicroorganisms, inter alia.

Examples of particularly advantageous components are the following:

Fungicides:

2-aminobutane; 2-anilino-4methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulphide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram,

dichlorophen, diclobutrazol, diclofluanid, diclomezine, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine,drazoxolon,

edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulphamide, flutolanil, flutriafol, folpet,fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax,myclobutanil,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin,piperalin, polycarbamate, polyoxin, probenazole, prochloraz,procymidone, propamocarb, propiconazole, propineb, pyrazophos,pyrifenox, pyrimethanil, pyroquilon,

quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thicyofen, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, trichlarnide, tricyclazole,tridemorph, triflumizole, triforine, triticonazole,

validamycin A, vinclozolin,

zineb, ziram.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb,buprofezin, butocarboxim, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimfos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonofos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion,ivermectin, lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulphenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, NI 25, nitenpyram,

omethoate, oxamyl, oxydemeton M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozine, pyrachlofos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxyfen,

quinalphos,

RH 5992,

salithion, sebufos, silafluofen, sulphotep, sulprofos,

tebufenozide, tebufenpyrad, tebupirimifos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiometon, thionazin, thuringiensin, tralomethrin,triarathene, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides, orwith fertilizers and growth-regulators is also possible.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agents are compounds which increase the action ofthe active compounds, without it being necessary for the synergisticagent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The active compounds according to the invention are not only activeagainst plant, hygiene and stored-product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites),such as ixodid ticks, argasid ticks, scab mites, trombiculid mites,flies (stinging and sucking), parasitic fly larvae, lice, hair lice,bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the sub-orders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order of the Diptera and the sub-orders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopyslla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabiusspp., Ixodes spp., Amblyomrma spp., Boophilus spp., Dermacentor spp.,Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

For example, they show a good retarding activity against Lucilla cuprinafly larvae and against Ctenocephalides felis flea eggs.

In addition, they affect the moulting of polyphagous ticks such asAmblyoma vanegatum.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which attack agriculturallivestock, such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese,honey bees, other domestic animals, such as, for example, dogs, cats,caged birds, aquarium fish, and so-called experimental animals, such as,for example, hamsters, guinea-pigs, rats and mice. By controlling thesearthropods, it is intended to reduce deaths and decreased performances(in meat, milk, wool, hides, eggs, honey and the like), so that moreeconomical and simpler animal keeping is made possible by using theactive compounds according to the invention.

In the veterinary sector, the active compounds according to theinvention are used in a known manner by enteral administration, forexample in the form of tablets, capsules, drinks, drenches, granules,pastes, boluses, the feed-through method, suppositories, by parenteraladministration, such as, for example, by means of injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal administration, forexample in the form of dipping or bathing, spraying, pouring-on andspotting-on, washing, dusting, and with the aid of shaped articles whichcomprise active compound, such as collars, ear tags, tail marks, limbbands, halters, marking devices and the like.

When administered to livestock, poultry, domestic animals and the like,the active compounds of the formula (I) can be used as formulations (forexample powders, emulsions, flowables) which comprise the activecompounds in an amount of 1 to 80% by weight, either directly or afterdilution by a factor of 100 to 10 000, or they may be used in the formof a chemical bath.

Furthermore, it has been found that the compounds of the formula (I)according to the invention have a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned by way of example and as beingpreferred, but without any limitation:

Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobiumpunctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobiumpertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctusafricanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendronspec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,Sinoxylon spec., Dinoderus minutus.

Dernapterans, such as Sirex juvencus, Urocerus gigas, Urocerus gigastaignus, Urocerus augur.

Termites, such as Kalotermes flavicollis, Cryptotermes brevis,Heterotermes indicola, Reticulitermes flavipes, Reticulitermessantonensis, Reticulitermes lucifugus, Mastotermes darwiniensis,Zootermopsis nevadensis, Coptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials are to be understood as meaning, in the presentcontext, non-live materials, such as, preferably, synthetic materials,glues, sizes, paper and board, leather, wood and timber products, andpaint.

The materials to be very particularly preferably protected againstattack by insects are wood and timber products.

Wood and timber products which can be protected by the compositionaccording to the invention or mixtures comprising such a composition areto be understood as meaning, for example, construction timber, woodenbeams, railway sleepers, bridge components, jetties, wooden vehicles,boxes, pallets, containers, telephone poles, wood lagging, windows anddoors made of wood, plywood, particle board, joiner's articles, or woodproducts which, quite generally, are used in the construction of housesor in joinery.

The active compounds can be used as such, in the form of concentrates orgenerally customary formulations, such as powders, granules, solutions,suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersant and/or binder or fixative, waterrepellent, if appropriate desiccants and UV stabilizers and, ifappropriate, colorants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for the protection ofwood and wooden materials comprise the active compound according to theinvention at a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thespecies and the occurrence of the insects and on the medium. The optimumrate of application can be determined upon use in each case by testseries. However, in general, it suffices to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be protected.

The solvent and/or diluent used is an organochemical solvent or solventmixture and/or an oily or oil-type organochemical solvent or solventmixture of low volatility and/or a polar organochemical solvent orsolvent mixture and/or water and, if appropriate, an emulsifier and/orwetting agent.

Organochemical solvents which are preferably employed are oily oroil-like solvents having an evaporation number of above 35 and aflashpoint of above 30° C., preferably above 45° C. Substances which areused as such oily and oil-like solvents which have low volatility andare insoluble in water are suitable mineral oils or their aromaticfractions, or mineral-oil-containing solvent mixtures, preferably whitespirit, petroleum and/or alkylbenzene.

Substances which are advantageously used are mineral oils with a boilingrange of 170 to 220° C., white spirit with a boiling range of 170 to220° C., spindle oil with a boiling range of 250 to 350° C., petroleumor aromatics of boiling range 160 to 280° C., essence of terpentine andthe like.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility and having anevaporation number of above 35 and a flashpoint of above 30° C.,preferably above 45° C., can be partially replaced by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flashpoint ofabove 30° C., preferably above 45° C., and that theinsecticide/fungicide mixture is soluble or emulsifiable in this solventmixture.

In a preferred embodiment, part of the organochemical solvent or solventmixture is replaced by an aliphatic polar organochemical solvent orsolvent mixture. Substances which are preferably used are aliphaticorganochemical solvents having hydroxyl and/or ester and/or ethergroups, such as, for example, glycol ether, esters and the like.

The organochemical binders used within the scope of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se and can be diluted with water and/or are soluble ordispersible or emulsifiable in the organochemical solvents employed, inparticular binders composed of, or comprising, an acrylate resin, avinyl resin, for example polyvinyl acetate, polyester resin,polycondensation or polyaddition resin, polyurethane resin, alkyd resinor modified alkyd resin, phenol resin, hydrocarbon resin, such asindene/coumarone resin, silicone resin, drying vegetable and/or dryingoils and/or physically drying binders based on a natural and/orsynthetic resin.

The artificial resin used as the binder can be employed in the form ofan emulsion, dispersion or solution. Up to 10% by weight of bitumen orbituminous substances can also be used as binder. In addition,colorants, pigments, water repellents, odour-masking substances andinhibitors or anticorrosives known per se and the like can also beemployed.

The composition or the concentrate preferably comprises, in accordancewith the invention, at least one alkyd resin or modified alkyd resinand/or a drying vegetable oil as the organochemical binder. Preferablyused according to the invention are alkyd resins with an oil content ofover 45% by weight, preferably 50 to 68% by weight.

All or some of the abovementioned binder can be replaced by a fixative(mixture) or a plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of binder employed).

The plasticizers are from the chemical classes of the phthalic esters,such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate,the phosphoric esters, such as tributyl phosphate, the adipic esters,such as di-(2-ethylhexyl) adipate, the stearates, such as butyl stearateor amyl stearate, the oleates, such as butyl oleate, the glycerol ethersor relatively high-molecular-weight glycol ethers, glycerol esters andp-toluene-sulphonic esters.

Fixatives are chemically based on polyvinyl alkyl ethers, such as, forexample, polyvinyl methyl ether, or ketones, such as benzophenone orethylenebenzophenone.

Particularly suitable as a solvent or diluent is also water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

Particularly effective protection of wood is achieved by large-scaleindustrial impregnation processes, for example vacuum, double-vacuum orpressure processes.

If appropriate, the ready-to-use compositions can additionally compriseother insecticides and, if appropriate, additionally one or morefungicides.

Suitable additional components which may be admixed are, preferably, theinsecticides and fingicides mentioned in WO 94/29 268. The compoundsmentioned in that document are expressly incorporated into the presentapplication by reference.

Very particularly preferred components which may be admixed areinsecticides, such as chlorpyrifos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron, and fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlofluanid, tolylfluanid,3-iodo-2-propinylbutyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and the use of the active compounds according to theinvention can be seen from the examples which follow.

PREPARATION EXAMPLES Example 1

(Process (a))

2.8 g (0.0067 mol) of2-(2,6-difluorophenyl)4-(4-trifluoromethoxybiphenyl-4-yl)-2-oxazolineand 6 g (0.013 mol) of phosphorus pentasulphide are stirred at 130° C.for 18 hours. After cooling, the reaction mixture is admixed with 100 mlof ice-water and, after addition of 40 ml of 45% strength aqueous sodiumhydroxide solution, stirred for 1 hour. The mixture is then extractedseveral times with 100 ml of dichloromethane each. The combined organicphases are washed repeatedly with dilute aqueous sodium hydroxidesolution (until a clear solution is obtained), dried over magnesiumsulphate and concentrated under reduced pressure.

1.8 g (62% of theory) of2-(2,6-difluorophenyl)-4-(4-trifluoromethoxybiphenyl-4-yl)-2-thiazolineof melting point 85-86° C. are obtained.

Using a method similar to Example 1 or following the general preparationinstructions, the following compounds of the formula (I) are obtained:

(I)

Ex. No. Ar¹ Ar² Physical data 2

m.p.: 109-10° C. 3

¹H-NMR (ppm in CDCl₃) 3.46(1H); 3.95(1H); 5.82(1H); 6.35-6.23(1H);7.74-6.97(aromatic H) 4

m.p.: 80-83° C. 5

m.p.: 65-66° C. 6

¹H-NMR (ppm in CDCl₃) 3.43(1H); 3.92(1H); 5.79(1H); 5.11-4.94(1H);7.73-7.29(aromatic H)

Use Examples Example A

Phaedon larvae test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with mustard beetle larvae (Phaedon cochleariae) while theleaves are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the beetle larvae have been killed; 0% means thatnone of the beetle larvae have been killed.

In this test, a destruction of 100% was brought about, after 7 days, forexample by the compounds of Preparation Examples 1, 2, 3 and 4 at anexemplary active compound concentration of 0.1%.

Example B

Plutella test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with caterpillars of the diamondback moth (Plutellamaculipennis) while the leaves are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, a destruction of 100% was brought about, after 7 days, forexample by the compounds of Preparation Examples 1, 2, 3, 4 and 5 at anexemplary active compound concentration of 0.1%.

Example C

Spodoptera test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with caterpillars of the owlet moth (Spodoptera frugiperda)while the leaves are still moist.

After the specified period of time, the action in % is determined. 100%means that all the caterpillars have been killed; 0% means that none ofthe caterpillars have been killed.

In this test, a destruction of 100% was brought about, after 7 days, forexample by the compounds of Preparation Examples 1, 3, 4 and 5 at anexemplary active compound concentration of 0.1%.

Example D

Myzus test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) heavily infested with green aphids(Myzus persicae) are dipped into the preparation of the active compoundof the desired concentration and placed into a plastic dish.

After the specified period of time, the destruction in % is determined.100% means that all the aphids have been killed; 0% means that none ofthe aphids have been killed.

In this test, a destruction of 80% or 98% was brought about, after 6days, for example by the compounds of Preparation Examples 1 and 3,respectively, at an exemplary active compound concentration of 0.1%.

Example E

Tetranychus test (OP resistant/dip treatment)

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted withemulsifier-containing water to the desired concentration.

Bean plants (Phaseolus vulgaris) heavily infested by all stages of thespider mite (Tetranychus urticae) are dipped into a preparation of theactive compound of the desired concentration.

After the specified period of time, the action in % is determined. 100%means that all the spider mites have been killed; 0% means that none ofthe spider mites have been killed.

In this test, a destruction of 98% was brought about, after 7 days, forexample by the compounds of Preparation Examples 1, 2, 3, 4 and 5 at anexemplary active compound concentration of 0.01%.

Example F

Panonychus test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted withemulsifier-containing water to the desired concentration.

Plum trees (Prunus domestica), about 30 cm in height and heavilyinfected by all stages of the fruit tree red spider mite (Panonychusulmi), are sprayed with a preparation of the active compound of thedesired concentration.

After the specified period of time, the action in % is determined. 100%means that all the spider mites have been killed; 0% means that none ofthe spider mites have been killed.

In this test, a destruction of 100% was brought about, after 7 days, forexample by the compounds of Preparation Examples 1, 2 and 3 at anexemplary active compound concentration of 0.02%.

Example G

Blowfly larvae test/development-inhibitory action

Test animals: Lucilia cuprina larvae

Emulsifier: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To produce a suitable preparation of active compound, 3 parts by weightof active compound are mixed with 7 parts by weight of theabovementioned mixture, and the resulting emulsion concentrate isdiluted with water to the desired concentration.

For each individual concentration, 30 to 50 larvae are introduced into atest tube which contains 1 cm³ of horse meat. 500 μl of the dilution tobe tested are pipetted onto this horse meat. The test tubes are placedin plastic beakers whose bottom is covered with sea sand, and kept in aclimatized room (26° C.±1.5° C., 70%±10% relative humidity). Theactivity is examined (larvicidal action) after 24 hours and again after48 hours. After emergence of the larvae (about 72 h), the test tubes areremoved and perforated plastic lids are fitted to the beakers. After 1.5times the development time (hatching of the control flies), the hatchedflies and the pupae/cocoons are counted.

The activity criterion is the incidence of death in treated larvae after48 h (larvicidal effect), or the inhibition of the hatching of adultsfrom pupae or the inhibition of pupa formation. The criterion for thein-vitro activity of a substance is the inhibition of the development ofthe flies, or a development standstill before the adult stage. 100%larvicidal action means that all the larvae have been killed after 48hours. 100% development-inhibitory action means that no adult flies havehatched.

In this test, an activity of 100% was shown, for example, by thecompounds of Preparation Examples 1, 2 and 3 at an exemplary activecompound concentration of 1000 ppm.

Example H

Test with cat fleas/development-inhibitory action

Test animals: Ctenocephalides felis (all stages: eggs, larvae, pupae andadults)

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

To produce a suitable preparation, 3 parts by weight of active compoundare mixed with 7 parts by weight of the abovementionedsolvent-emulsifier mixture, and the resulting emulsion concentrate isdiluted with water to the desired concentration.

200 ml of this active compound preparation are added to 1.8 g of culturemedium (blood meal medium: 125 parts of sea sand, 20 parts of rat food,3 parts of blood meal, 2 parts of dry yeast) in disposable test tubes(Ø2.0 cm), homogenized and dried overnight. The medium is then chargedwith a spatula-tipful of sieved flea eggs (obtained from artificiallyinfected cats).

For up to 1.5 times the development time of the control experiment, theactivity of the active compound preparation is determined every 2 daysby examining the experiments for flea development stages.

The criterion for the in-vitro activity of a substance is the inhibitionof the development of the fleas, or a development standstill before theadult stage. 100% means that no adult fleas developed; 0% means thatadult fleas hatched.

In this test, an activity of 100% was shown, for example, by thecompound of Preparation Example 1 at an exemplary active compoundconcentration of 1000 ppm.

Example I

Ecdysis test on polyphagous tick nymphs

Test animals: Amblyomma variegatum ticks which have sucked themselvesfull

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

To produce a suitable formulation, 3 parts by weight of active compoundare mixed with 7 parts of the abovementioned solvent-emulsifier mixture,and the resulting emulsion concentrate is diluted with water to theconcentration desired in each case.

10 nymphs which have sucked themselves full are immersed for 1 minuteinto the preparation of active compound to be tested. The animals aretransferred to petri dishes (Ø9.5 cm) which are equipped withfilter-paper discs and covered. After the nymphs have remained in acontrolled-environment cabinet for 4 weeks, the ecdysis rate isdetermined.

100% means that none of the animals have undergone normal ecdysis; 0%means that all the animals have undergone normal ecdysis.

In this test, an activity of 100% was shown, for example, by thecompound of Preparation Example 2 at an exemplary active compoundconcentration of 1000 ppm.

What is claimed is:
 1. Compounds of the formula (IB)

in which Ar¹ represents the following phenyl radicals:

R² represents hydrogen, C₁₋₁₂-alkyl or C₃-C₁₂-alkenyl, orC₃-C₁₂-alkinyl, or C₁-C₆-halogenoalkyl having one or more fluorineand/or chlorine atoms, or C₃-C₆-cycloalkyl orC₃-C₆-cycloalkyl-C₁-C₄-alkyl, each of which is optionally mono- orpolysubstituted in the cycloalkyl moiety by identical or differentsubstituents from the group consisting of: halogen, C₁-C₄-alkyl,C₂-C₄-alkenyl which is optionally mono- or polysubstituted by halogen,and phenyl or styryl, each of which is optionally mono- orpolysubstituted, by halogen; or represents C₄-C₆-cycloalkenyl orC₄-C₆-cycloalkenyl-C₁-C₄-alkyl, each of which is optionally mono- orpolysubstituted by identical or different halogen and/or C₁-C₄-alkylsubstituents; or represents phenyl-C₁-C₄-alkyl or naphthylmethyl, eachof which is optionally mono- or polysubstituted in the aryl moiety byidentical or different substituents from the group consisting of:halogen, C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl having one or more fluorineand/or chlorine atoms, C₁-C₁₂-alkoxy and C₁-C₁₂-halogenoalkoxy havingone or more fluorine and/or chlorine atoms; or represents the radical—COR³ where R³ represents C₁-C₁₂-alkyl, or C₁-C₁₂-alkoxy, orC₃-C₁₂-alkenyl, or C₃-C₁₂-alkenyloxy, or represents C₃-C₆-cycloalkyl,C₃-C₁₀-cycloalkyloxy or C₃-C₁₀-cycloalkyl-C₁-C₆-alkoxy, each of which isoptionally mono- or polysubstituted in the cycloalkyl moiety byidentical or different substituents from the group consisting of:C₁-C₄-alkyl, halogen, C₁-C₄-halogenoalkyl having one or more fluorineand/or chlorine atoms and C₂-C₄-halogenoalkenyl having one or morefluorine and/or chlorine atoms; or represents phenyl or naphthyl, eachof which is optionally mono- or polysubstituted by identical ordifferent substituents from the group consisting of: halogen,C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl having one or more fluorine and/orchlorine atoms, C₁-C₁₂-alkoxy and C₁-C₁₂-halogenoalkoxy having one ormore fluorine and/or chlorine atoms; or represents the radical —NR⁴—R⁵where R⁴ represents hydrogen or C₁-C₁₂-alkyl and R⁵ representsC₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl having one or more fluorine and/orchlorine atoms, or C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₄-alkyl,each of which is optionally mono- or polysubstituted in the cycloalkylmoiety by identical or different substituents from the group consistingof: C₁-C₄-alkyl, halogen, C₁-C₄-halogenoalkyl having one or morefluorine and/or chlorine atoms and C₂-C₄-halogenoalkenyl having one ormore fluorine and/or chlorine atoms; or represents phenyl orphenyl-C₁-C₆-alkyl, each of which is optionally mono- orpolysubstituted, by identical or different substituents from the groupconsisting of: halogen, C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl having one ormore fluorine and/or chlorine atoms, C₁-C₁₂-alkoxy andC₁-C₁₂-halogenoalkoxy having one or more fluorine and/or chlorine atoms;or represents the radical —C(R⁶R⁷)—C(R⁸)═NOR⁹ where R⁶ and R⁷ areidentical or different and represent hydrogen or C₁-C₄-alkyl, R⁸represents hydrogen, C₁-C₄-alkyl or C₃-C₆-cycloalkyl which is optionallymono-, di- or trisubstituted by identical or different substituents fromthe group consisting of C₁-C₄-alkyl, halogen or C₁-C₄-halogenoalkyl andR⁹ represents C₁-C₄-alkyl, except the compounds:


2. Compounds of the formula (IB) according to claim 1 in which R²represents halogenoalkyl.
 3. Processes for preparing compounds of theformula (I),

in which Ar¹ and Ar² each represent independently of one anotheroptionally substituted phenyl; said processes comprising a) reactingcompounds of the formula (II)

in which Ar¹ and Ar² each have the meanings above, with a sulphurizingagent, optionally in the presence of a diluent; or b) reacting compoundsof the formula (Ia)

in which Ar¹ has the meaning given above; and Ph represents optionallysubstituted halogenophenyl; with boronic acids of the formula (III)Ph¹—B(OH)₂   (III) in which Ph¹ represents optionally substitutedphenyl; in the presence of a base, optionally in the presence of acatalyst and in the presence of a diluent.
 4. A pesticidal compositioncomprising a pesticidally effective amount of at least one compoundaccording to claim 1 and an extender and/or surface active agent.
 5. Amethod of combating pests comprising applying a pesticidally effectiveamount of at least one compound according to claim 1 to the pests and/ortheir habitat and/or to a location from which it is desired to excludesuch pests.
 6. A process for preparing a pesticidal compositionaccording to claim 4 comprising mixing said compound with said extenderand/or surface active agent.
 7. A compound according to claim 1, whichhas the formula


8. A compound according to claim 1, which has the following structure:


9. A compound according to claim 1, which has the following structure:


10. A compound according to claim 1, which has the following structure:


11. A compound according to claim 1, which has the following structure:


12. A compound according to claim 1, which has the following structure: